Patent GB-569037-A (GB)
Title: Preparation of organic antimony compounds
IPC: C07F9/92
Filed: 1940-06-10
Abstract: Organo-antimony compounds are prepared by reacting a tervalent antimony compound containing halogen with a diazonium halide in the presence of an organic solvent and of copper or a copper compound as catalyst.  To produce monoaryl products, an antimony trihalide is reacted with the diazonium halide, whereby aryl antimony tetrahalides are formed.  By reacting an aryl halogenostilbine with a diazonium halide under the same conditions, products containing more than one aryl group attached to antimony are obtained.  The antimony trihalide and the diazonium halide may be present as an addition compound, or the diazonium halide may be used in the form of its double compound with a zinc halide.  The catalyst is preferably a cuprous compound, e.g. cuprous chloride, and suitable solvents mentioned are alcohol, acetone, methylethyl ketone and ethyl acetate.  The resulting aryl antimony tetrahalides may be reduced, e.g. by means of sulphur dioxide, to aryl dihalogenostibines for use in the preparation of products containing more than one aryl group, or may be converted into aryl stibinic acids by treatment with caustic alkali solution. For the preparation of di-aryl products, an aryl di-halogenostibine is reacted with the double salt of a zinc halide and a diazonium halide; the product is a diaryl antimony trihalide, which may either be converted into the corresponding diaryl stibonic acid by treatment with caustic alkali solution or reduced to a diaryl halogenostibine. By reacting the latter compounds with the double salt of a zinc halide and a diazonium halide, triarylantimony dihalides are produced.  Examples are given of: (1) the production of phenyl stibinic chloride from diazotised aniline and antimony trichloride, and its conversion into diphenyl stibonic acid by reduction followed by interaction with zinc chloride-benzene diazonium chloride and treatment with sodium hydroxide solution; (2) the preparation of p-chlorphenyl, p-toluene, m-nitrophenyl and a - and b -naphthyl stibinic chlorides from antimony chloride and diazotised p-chloraniline, p-toluidine, m-nitraniline and a - and b -naphthylamines respectively; the p-chlorphenyl stibinic chloride is poured into caustic soda solution to give the stibinic acid; (3) the preparation of diphenyl antimony trichloride by reduction of phenyl stibinic chloride and treatment with zinc chloridebenzene diazonium chloride; reduction of the resulting trichloride, followed by treatment with more of the double salt, gives rise to triphenyl antimony dichloride; (4) the production of di-a -naphthyl chlorostibine by reducing a -naphthyl stibinic chloride, treating the dichlorostibine so obtained with zinc chloro-a -naphthyl diazonium chloride and reducing the resulting di-a -naphthyl stibinic chloride; the di-b -naphthyl compound is obtained similarly; (5) the preparation of phenyl-a -naphthyl stibinic chloride by reacting phenyl dichlorostibine with zinc chloride-a -naphthyl diazonium chloride; the product may be converted into the phenyl-a -naphthyl stibonic acid; phenyl-b -naphthyl stibinic chloride is prepared in an analogous manner.